This invention is related to the preparation of methylene and oxymethylene bis-esters by carbonylation reactions in the presence of transition metal catalysts.
Applicants' U.S. Pat. No. 3,720,706, issued Mar. 13, 1973, and U.S. Ser. No. 302,373, filed Oct. 30, 1972, disclose the preparation of methylene and oxymethylene bis-esters by the reaction of a carboxylic acid, ethylene, carbon monoxide and formaldehyde in the presence of a rhodium catalyst and an iodide or bromide promoter. U.S. Pat. No. 3,702,706 and U.S. Ser. No. 302,373 also disclose the preparation of methylene and oxymethylene bis-propionates directly from ethylene, carbon monoxide, water and formaldehyde in the presence of a rhodium catalyst and an iodide or a bromide promoter.
Tomiska and Spousta, Angew Chem., Int. Ed., 1, 211 (1962) disclose the preparation of methylene and oxymethylene bis-acetates from acetic anhydride and trioxane in the presence of perchloric acid.
Methylene and oxymethylene bis-esters are useful for preserving moist grain during storage, as disclosed by French Pat. No. 70/37,979 of Kensler et al, granted July 12, 1971.